Mannich condensation products useful as sequestering agents

ABSTRACT

The present invention is directed to Mannich condensation product sequestering agents or mixtures of Mannich condensation product sequestering agents for use in fuels and lubricating oils. The present invention is also directed to a process for preparing the Mannich condensation product sequestering agents. The present invention is also directed to a product formed by combining, under reaction conditions, a polyisobutyl-substituted hydroxyaromatic compound, an aldehyde, an amino acid or ester thereof, and an alkali metal base to form the Mannich condensation product sequestering agent. The present invention is also directed to a lubricating oil composition, a lubricating oil concentrate, a fuel composition, and a fuel concentrate having the Mannich condensation product sequestering agents of the present invention.

FIELD OF THE INVENTION

The present invention is directed to Mannich condensation productsequestering agents or mixtures of Mannich condensation productsequestering agents for use in fuels and lubricating oils. The presentinvention is also directed to a process for preparing the Mannichcondensation product sequestering agents. The present invention is alsodirected to a product formed by combining, under reaction conditions, apolyisobutyl-substituted hydroxyaromatic compound, an aldehyde, an aminoacid or ester thereof, and an alkali metal base to form the Mannichcondensation product sequestering agent. The present invention is alsodirected to a lubricating oil composition, a lubricating oilconcentrate, a fuel composition, and a fuel concentrate having theMannich condensation product sequestering agents of the presentinvention.

BACKGROUND OF THE INVENTION

Lubricating oils contain additives that perform many importantfunctions. Ashless dispersants are added to lubricating oils to dispersevarnish, lacquer, and sludge that may be formed in the oil and preventthe formation of deposits. Ashless dispersants also disperse soot andprevent viscosity buildup caused by the agglomeration of soot in theoil. Overbased detergents are added to lubricating oils to neutralizeacids. These acids can cause wear and corrosion, and can cause acidcatalyzed reactions and rearrangements to occur in the oil.Anti-oxidants are added to lubricating oils to control oxidation of theoil by scavenging radicals or by decomposing hydroperoxides that areformed from the oxidation of the oil. Wear inhibitors are added tolubricating oils to prevent wear of the metal parts caused by friction.Other additives such as corrosion inhibitors, friction modifiers,viscosity index improvers, pour point depressants, seal, swell agents,etc., can also be added to lubricating oils to provide importantproperties to the finished lubricant.

Metal ions can play an important role in the deterioration oflubricating oils. Transition metals such as Fe⁺³, Cu⁺², Pb⁺², and othermetals, can catalyze the oxidation of the oil resulting in the formationof the primary oxidation products such as hydroperoxides, carboxylicacids, carbonyl compounds, hydroxyl carbonyl compounds, and the like. Inaddition, metal ions such as Fe⁺³, Cu⁺², Pb⁺², and other metals, cancatalyze the polymerization of the primary oxidation products resultingin the formation of sludge, lacquer, and varnish.

In order to prevent the metal catalyzed oxidation and polymerization oflubricating oils, it would be desirable to find a way to complex orsequester the metal ions and prevent the metal ions from acting asoxidation and polymerization catalysts.

Sequestering agents have many uses, in living plants for supplyingnecessary trace elements, in metal plating baths, removing rust stains,removing impurities and in fuels and lubricating oils. Most well knownsequestering agents are useful only in aqueous media. There is a greatneed for good sequestering agents that are oil-soluble. Oil-solublesequestering agents are also useful for the introduction of metals intonon-aqueous systems, for providing oil-borne micro-nutrients to plantsand many other uses known to persons skilled in the art. Oils useful forlubricating internal combustion engines are generally either mineraloils or synthetic oils of lubricating viscosity. Thus, sequesteringagents for use in lubricating oils or hydrocarbon fuels must beoil-soluble.

The conventional oil-soluble Mannich condensation products are useful ininternal combustion engine fuels. Non-volatile constituents of fuel,such as additives, sometimes form deposits or varnish on inlet valvesand on heating elements. Such deposits and varnish impair the efficiencyof these elements. In addition, fuels are susceptible to chemicalreactions, such as, oxidation, on aging. One effect of oxidation is toproduce soluble and insoluble materials that form deposits whichinterfere with the proper functioning of the internal combustionengines. The conventional oil-soluble Mannich condensation products helpto reduce deposits.

Oil-soluble Mannich condensation products are also useful in internalcombustion engine lubricating oils. These products generally act asdispersants to disperse sludge, varnish, and lacquer, and prevent theformation of deposits. In general, conventional oil-soluble Mannichcondensation products are formed from the reaction ofpolyisobutyl-substituted phenols with formaldehyde and an amine or apolyamine. These products have limited ability to sequester Fe⁺³ andhave limited ability to prevent the Fe⁺³ catalyzed oxidation andpolymerization that often occur.

Water soluble Mannich condensation products are well known assequestering agents. However, such products cannot be used assequestering agents in fuels and lubricating oils.

The preparation of Mannich condensation products is well known in theart. A number of patents disclose Mannich condensation products ofalkylphenols, aldehydes and amines. However, none of the known Mannichcondensation products contain both the needed oil solubility and theability to sequester Fe⁺³ to prevent Fe⁺³ catalyzed oxidation andpolymerization reaction in lubricating oil.

U.S. Pat. No. 4,032,304 discloses an improved fuel compositioncontaining a normally liquid fuel, a carboxylic acid ester oflubricating viscosity and an oil-soluble nitrogen-containing dispersant.The dispersant is characterized by the presence therein of asubstantially saturated hydrocarbon-based radical having at least 50carbon atoms. The dispersant is preferably a carboxylic dispersant or aMannich-type dispersant. The Mannich-type dispersant is for example thereaction product of an alkylphenol with formaldehyde and a polyethylenepolyamine.

U.S. Pat. No. 4,069,249 discloses a novel Mannich condensation productchelating agent for iron (III) or iron (II). The chelating agent is aMannich condensation product made from phenol or substituted-phenol,formaldehyde, a di-amino di-acid and a di-amine. The process for makingthese Mannich condensation products is disclosed in U.S. Pat. No.4,338,460.

U.S. Pat. No. 4,166,726 discloses a fuel additive and fuel composition.The additive compound is a mixture of a polyisobutylene amine and thereaction product of an alkylphenol, an aldehyde and an amine. Theadditive provides surprising stability in preventing thermal degradationof fuels, particularly fuels for compression ignition engines.

U.S. Pat. No. 4,116,991 discloses an aromatic chelating agent having ahydroxyl group at the center of the molecule. Such chelating agents havebetter stability in an alkaline environment.

U.S. Pat. No. 4,130,582 discloses a process for the preparation ofphenolic ethylenediamine polycarboxylic acids in predominantly the orthoisomeric form which comprises reacting a phenol compound,ethylenediamine, glyoxylic acid and a base, said phenol compoundfunctioning both as a reactant and as a solvent for the reaction system.

U.S. Pat. No. 4,197,091 discloses a composition for inhibiting thecorrosion of ferrous metal pipelines used to transport petroleumhydrocarbons comprising a major portion of a mixture of C₃₆di-carboxylic dimer acid and a C₅₄ trimer acid, which mixture has anacid number of at least 110 and from 0.5 up to 5% of a composition fromthe group consisting of (a) anN,N′-di(ortho-hydroxyarylidene)-1,2-alkyldiamine in which the arylideneradical contains 6-7 carbon atoms and the alkylene radical contains 2-3carbon atoms; and (b) a polymeric condensation product obtained by thereaction of a phenol having two reactive ring positions, a loweraliphatic aldehyde and a polyamine.

U.S. Pat. No. 4,225,502, a division of application Ser. No. 630,792,U.S. Pat. No. 4,069,249 discussed above, discloses a novel Mannichcondensation product chelating agent for iron (III) or iron (II). Thechelating agent is a Mannich condensation product made from phenol orsubstituted-phenol, formaldehyde, a di-amino di-acid and a di-amine. Thesingle claim is to a cyano-substituted compound.

U.S. Pat. No. 4,200,545 discloses combinations of amino phenols, whereinsaid phenols contain a substantially saturated hydrocarbon substituentof at least 10 aliphatic carbon atoms, and one or moredetergent/dispersants selected from the group consisting of (I) neutralor basic metal salts of an organic sulfur acid, phenol or carboxylicacid; (II) hydrocarbyl-substituted amines wherein the hydrocarbylsubstituent is substantially aliphatic and contains at least 12 carbonatoms; (III) acylated nitrogen-having compounds having a substituent ofat least 10 aliphatic carbon atoms; and (IV) nitrogen-having condensatesof a phenol, aldehyde and amino compound. Fuels and lubricants havingsuch combinations as additives are particularly useful in two-cycle(two-stroke) engines.

U.S. Pat. No. 4,387,244 discloses that alkyl-substituted hydroxybenzylamino acid oligomers are effective metal chelating agents in a broadrange of non-aqueous systems. The products claimed display surprisinglyhigh solubilities in a broad range of substituted and unsubstitutedaliphatic and aromatic solvents.

U.S. Pat. No. 4,655,949 discloses a novel lubricating oil compositioncomprising an organometallic additive, including a metal selected fromGroups I, Ib and VIII of the Periodic System of Elements, e.g. Na, K,Cu, Co, Ni or Fe, chelated with the reaction product of formaldehyde, anamino acid and a phenol, dissolved in a lubricating oil. Depending onthe choice of metal, the above organometallic additive imparts rustinhibition, sludge dispersant, wear reduction and anti-oxidantproperties to the said lubricating oil.

U.S. Pat. No. 4,734,212 discloses Bis-Mannich base deposit inhibitors;lubricating oil compositions having these inhibitors and a process forpreparing these inhibitors.

U.S. Pat. No. 4,847,415 discloses certain Mannich reaction products(i.e. alkylated phenol, polyoxyalkylenediamine, and an aldehyde) whichare used to deactivate iron species already present in hydrocarbonfluids. Left untreated, such iron species lead to decompositionresulting in the formation of gummy, polymer masses in the hydrocarbonliquid. The method for the preparation of these Mannich condensationproducts are claimed in the divisional U.S. Pat. No. 4,883,580.

U.S. Pat. No. 4,894,139 discloses certain Mannich reaction productsformed from the reaction of an alkyl-substituted catechol, a polyamineand an aldehyde which are used to deactivate copper metal speciescontained in hydrocarbon fluids. Left untreated, such species lead todecomposition resulting in the formation of gummy, polymer masses in thehydrocarbon liquid.

U.S. Pat. No. 5,122,161 discloses a diesel fuel composition comprising(a) a major portion of a diesel fuel, and (b) a minor amount, as adiesel fuel injector detergent, of a glycolated Mannich coupled productof bis-polyisobutylene succinimide of a polyamine, prepared by: (i)reacting an alkylsuccinic acid anhydride with a polyamine to form abis-succinimide; (ii) reacting the bis-succinimide with a phenol in thepresence of an aldehyde to form a Mannich phenol coupled bis-succinimideproduct; (iii) glycolating the Mannich phenol coupled bis-succcinimideproduct with glycolic acid to form a glycolated Mannich phenol coupledbis-succinimide product; and (iv) recovering the glycolated Mannichphenol coupled bis-succinimide product.

U.S. Pat. No. 5,641,394 discloses a composition for use in deactivatingiron species in hydrocarbon fluids, comprising the products resultingfrom the reaction of (I) a substituted-catechol, (II) a mixture ofpolyamines, and (III) an aldehyde. The composition also functions as ananti-oxidant in hydrocarbon fluids. The anti-oxidant function isseparate from, and in addition to the metal deactivating properties ofthe invention. These functional properties of the invention can acteither singly, or in concert, for stabilization of hydrocarbon fluids.

An article titled “Preparation of AmphiphilicPolyisobutylenes-b-polyethylenamines by Mannich Reaction. III. Synthesisof Polyisobutylenes-b-polyethylenamines,” by J. D. Jamois, M. Tessierand E. Marechal, Journal of Polymer Science Part A: Polymer Chemistry,Vol. 31, 1959-1966 (1993) discloses preparation of copolymersassociating alpha-phenololigoisobutylene and triethylenetetramine blocksin the same chain by reacting aqueous formaldehyde withalpha-phenololigoisobutylene and triethylenetetramine.

SUMMARY OF THE INVENTION

The present invention is directed to a Mannich condensation productsequestering agent or mixtures of Mannich condensation productsequestering agents for use in fuels and lubricating oils. The presentinvention is also directed to a method for preparing the Mannichcondensation product sequestering agents. The present invention is alsodirected to a product formed by combining, under reaction conditions, apolyisobutyl-substituted hydroxyaromatic compound, an aldehyde, an aminoacid or ester thereof, and an alkali metal base to form the Mannichcondensation product sequestering agent. The present invention is alsodirected to a lubricating oil composition, a lubricating oilconcentrate, a fuel composition, and a fuel concentrate having theMannich condensation product sequestering agents of the presentinvention.

Accordingly, the present invention is directed to a Mannich condensationproduct prepared by the Mannich condensation of:

-   -   (a) a polyisobutyl-substituted hydroxyaromatic compound, wherein        the polyisobutyl group is derived from polyisobutene containing        at least about 50 weight percent methylvinylidene isomer and has        a number average molecular weight in the range of from about 400        to about 5,000;    -   (b) an aldehyde;    -   (c) an amino acid or ester derivative thereof; and    -   (d) an alkali metal base.

In another embodiment the present invention is directed to a Mannichcondensation product prepared by the Mannich condensation of:

-   -   (a) a polyisobutyl-substituted hydroxyaromatic compound having        the formula:

-   -   -   wherein R₁ is a polyisobutyl group derived from            polyisobutene containing at least 50 weight percent            methylvinylidene isomer and having a number average            molecular weight in the range of about 400 to about 5,000,            R₂ is hydrogen or lower alkyl having one carbon atom to            about 10 carbon atoms, and R₃ is hydrogen or —OH;

    -   (b) a formaldehyde or an aldehyde having the formula:

-   -   -   wherein R′ is branched or linear alkyl having one carbon            atom to about 10 carbon atoms, cycloalkyl having from about            3 carbon atoms to about 10 carbon atoms, aryl having from            about 6 carbon atoms to about 10 carbon atoms, alkaryl            having from about 7 carbon atoms to about 20 carbon atoms,            or aralkyl having from about 7 carbon atoms to about 20            carbon atoms;

    -   (c) an amino acid or ester derivative thereof having the        formula:

-   -   -   wherein W is —[CHR″]—_(m) wherein each R″ is independently            H, alkyl having one carbon atom to about 15 carbon atoms, or            a substituted-alkyl having one carbon atom to about 10            carbon atoms and one or more substituents selected from the            group consisting of amino, amido, benzyl, carboxyl,            hydroxyl, hydroxyphenyl, imidazolyl, imino, phenyl, sulfide,            or thiol; and m is an integer from one to 4, and A is            hydrogen or alkyl having one carbon atom to about 6 carbon            atoms; and

    -   (d) an alkali metal base.

In general, the principal Mannich condensation product of the inventioncan be represented by the formula:

wherein each R is independently —CHR′—, wherein R′ is as defined above,R₁ is a polyisobutyl group derived from polyisobutene containing atleast 50 weight percent methylvinylidene isomer and having a numberaverage molecular weight in the range of about 400 to about 5,000;

X is hydrogen, an alkali metal ion or alkyl having one to about 6 carbonatoms;

W is —[CHR″]—_(m) wherein each R″ is independently H, alkyl having onecarbon atom to about 15 carbon atoms, or a substituted-alkyl having onecarbon atom to about 10 carbon atoms and one or more substituentsselected from the group consisting of amino, amido, benzyl, carboxyl,hydroxyl, hydroxyphenyl, imidazolyl, imino, phenyl, sulfide, or thiol;and m is an integer from one to 4;

Y is hydrogen, alkyl having one carbon atom to about 10 carbon atoms,—CHR′OH, wherein R′ is as defined above,

or

-   -   wherein Y′ is —CHR′OH, wherein R′ is as defined above; and R, X,        and W are as defined above;

Z is hydroxyl, a hydroxyphenyl group of the formula:

-   -   wherein R, R₁, Y′, X, and W are as defined above,        and n is an integer from 0 to 20, with the proviso that when        n=0, Z must be:

-   -   wherein R, R₁, Y′, X, and W are as defined above.

Preferably the R₁ polyisobutyl group has a number average molecularweight of about 500 to about 2,500. More preferably the R₁ polyisobutylgroup has a number average molecular weight of about 700 to about 1,500.Most preferably the R₁ polyisobutyl group has a number average molecularweight of about 700 to about 1,100.

Preferably the R₁ polyisobutyl group is derived from polyisobutenecontaining at least about 70 weight percent methylvinylidene isomer andmore preferably the R₁ polyisobutyl group is derived from polyisobutenecontaining at least 90 weight percent methylvinylidene isomer.

In the compound of formula I above, preferably X is hydrogen, morepreferably an alkali metal ion and most preferably a sodium ion.

In another embodiment of the invention, in the compound of formula Iabove, X is alkyl selected from methyl or ethyl.

In a preferred embodiment of the Mannich condensation product of thepresent invention R is CH₂, R₁ is derived from polyisobutene containingat least 50 weight percent methylvinylidene isomer and a number averagemolecular weight in the range of about 700 to about 1,100, W is CH₂; Xis sodium ion and n is 0 to 20.

Another embodiment of the present invention is directed to a method forpreventing metal ion catalyzed oxidation and polymerization reactions ina hydrocarbon medium comprising sequestering the metal ion by theaddition of an effective amount of the Mannich condensation product ofthe present invention, as described above. The method for preventingmetal ion catalyzed oxidation and polymerization reactions isparticularly suitable for sequestering the metal ion by the addition ofan effective amount of the Mannich condensation product of the presentinvention in engine oil.

The present invention is also directed to a product formed by combining,under reaction conditions, a polyisobutyl-substituted hydroxyaromaticcompound, an aldehyde, an amino acid or amino acid ester, and an alkalimetal base to form the Mannich condensation product sequestering agent.

Another embodiment of the present invention is directed to a process forpreparing a Mannich condensation product comprising reacting apolyisobutyl-substituted hydroxyaromatic compound, wherein thepolyisobutyl moiety is derived from polyisobutene containing at least 50weight percent methylvinylidene isomer and a number average molecularweight in the range of about 400 to about 5,000, an aldehyde, an aminoacid or amino acid ester and optionally a diluent, in the presence of abase.

Preferably the polyisobutyl-substituted hydroxyaromatic compound ispolyisobutyl-substituted phenol wherein the polyisobutyl moiety isderived from polyisobutene containing at least 70 weight percentmethylvinylidene isomer and more preferably the polyisobutyl moiety isderived from polyisobutene containing at least 90 weight percentmethylvinylidene isomer.

Preferably the aldehyde is formaldehyde or paraformaldehyde. Morepreferably the aldehyde is paraformaldehyde.

Preferably the diluent is an alkanol having one carbon atom to about 10carbon atoms. More preferably the alkanol is methanol.

Preferably the base is an alkali metal hydroxide. More preferably thealkali metal hydroxide is sodium hydroxide.

The amino acid or ester derivative thereof has the formula

-   -   wherein W are as defined above and A is hydrogen or alkyl having        one carbon atom to about 6 carbon atoms.

Preferably the amino acid is glycine.

In the above process the amino acid may be added in the form of itsalkali metal ion salt. Preferably the alkali metal ion is a sodium ionor a potassium ion, more preferably the alkali metal ion is a sodiumion.

A further embodiment of the present invention is directed to alubricating oil composition comprising a major amount of an oil oflubricating viscosity and a minor effective amount of one or more of theabove described Mannich condensation products of the present invention.

A further embodiment of the present invention is directed to alubricating oil concentrate comprising about 20 percent to 80 percent ofa diluent oil of lubricating viscosity and an effective amount of one ormore of the above described Mannich condensation products of the presentinvention. Both the lubricating oil composition and the lubricating oilconcentrate may contain other additives designed to improve theproperties of the lubricating oil.

A further embodiment of the present invention is directed to a fuelcomposition comprising a major amount of hydrocarbons boiling in thegasoline or diesel range and a minor effective amount of one or more ofthe above described Mannich condensation products of the presentinvention which has been further reacted to remove/replace any alkalimetal. In general it is not desirable for a fuel additive composition tocontain ash. Therefore, it is desirable to react the above describedMannich condensation products of the present invention in such a waythat any alkali metal salt present is converted to an ammonium or otherappropriate salt giving an ashless Mannich condensation product.

A further embodiment of the present invention is directed to a fuelconcentrate comprising an inert stable oleophilic organic solventboiling in the range of from about 65° C. to about 204° C. and fromabout 10 weight percent to about 90 weight percent of one or more of theabove described Mannich condensation product of the present inventionwhich has been further reacted to remove/replace any alkali metalpresent.

The Mannich condensation products of the present invention may also beemployed as dispersants in lubricating oil. For use as dispersants infuels the alkali metal ions in Mannich condensation products arereplaced with ammonium ions.

Among other factors, the present invention is based upon the discoverythat the Mannich condensation products of the present invention areeffective in sequestering metals, especially Fe⁺³, and preventing metalion catalyzed oxidation and polymerization reactions, while maintainingsufficient oil solubility for use in lubricating oils and fuels.

DETAILED DESCRIPTION OF THE INVENTION Definitions

As used herein, the following terms have the following meanings unlessexpressly stated to the contrary:

The term “aldehydes” as used herein refer to formaldehyde or aldehydeshaving the formula

wherein R′ is branched or linear alkyl having from one carbon atom toabout 10 carbon atoms, cycloalkyl having from about 3 carbon atoms toabout 10 carbon atoms, aryl having from about 6 carbon atoms to about 10carbon atoms, alkaryl having from about 7 carbon atoms to about 20carbon atoms, or aralkyl having from about 7 carbon atoms to about 20carbon atoms.

Representative aldehydes for use in the preparation of the Mannichcondensation products of the present invention include, but are notlimited to aliphatic aldehydes such as formaldehyde, acetaldehyde,propionaldehyde, butyraldehyde, valeraldehyde, caproaldehyde andheptaldehyde. Aromatic aldehydes are also contemplated for use in thepreparation of the Mannich condensation products of the presentinvention, such as benzaldehyde and alkylbenzaldehyde. Para-tolualdehydeis an example of an alkylbenzaldehyde. Also useful are formaldehydeproducing reagents, such as paraformaldehyde and aqueous formaldehydesolutions such as formalin. Aldehydes most preferred for use in the inthe preparation of the Mannich condensation products of the presentinvention are paraformaldehyde and formalin.

Aldehydes most preferred for use in the in the preparation of theMannich condensation products of the present invention areparaformaldehyde and formalin.

Preferably the aldehyde is formaldehyde. By formaldehyde is meant allits forms, including gaseous, liquid and solid. Examples of gaseousformaldehyde is the monomer CH₂O and the trimer, (CH₂O)₃ (trioxane)having the formula given below.

Examples of liquid formaldehyde are the following:

-   -   1. Monomer CH₂O in ethyl ether.    -   2. Monomer CH₂O in water which has the formulas CH₂(H₂O)₂        (methylene glycol) and HO(—CH₂O)_(n)—H.    -   3. Monomer CH₂O in methanol which has the formulas OHCH₂OCH₃ and        CH₃O(—CH₂O)_(n)—H.

Formaldehyde solutions are commercially available in water and variousalcohols. In water it is available as a 37%-50% solution. Formalin is a37% solution in water.

Formaldehyde is also commercially available as linear and cyclic(trioxane) polymers. Linear polymers may be low molecular weight or highmolecular weight polymers.

The term “alkali metal” as used herein refers to Group I A metals of thePeriodic Table, such as lithium, sodium and potassium.

The term “amino acid or ester derivative thereof” as used herein refersto amino acids having the formula

-   -   wherein W is —[CHR″]—_(m) wherein each R″ is independently H,        alkyl having one carbon atom to about 15 carbon atoms, or a        substituted-alkyl having one carbon atom to about 10 carbon        atoms and one or more substituents selected from the group        consisting of amino, amido, benzyl, carboxyl, hydroxyl,        hydroxyphenyl, imidazolyl, imino, phenyl, sulfide, or thiol; and        m is an integer from one to 4, and A is hydrogen or alkyl having        one carbon atom to about 6 carbon atoms. Preferably the alkyl is        methyl or ethyl.

The term “amino acid salt” as used herein refers to salts of amino acidshaving the formula

-   -   wherein W is as defined above and M is an alkali metal ion.        Preferably M is a sodium ion or a potassium ion. More preferably        X is a sodium ion.

The term “base” as used herein refers to alkali metal hydroxides andalkali metal alkoxides. Preferably the base is an alkali metal hydroxideselected from the group consisting of sodium hydroxide, lithiumhydroxide or potassium hydroxide. More preferably the alkali metalhydroxide is sodium hydroxide or potassium hydroxide.

The term “color test” as used herein refers to the color test used fordetermination of the ability of the Mannich condensation products of thepresent invention to sequester Fe⁺³ ions. The test is briefly describedbelow:

Test for Iron Sequestering Ability

The test used for iron sequestering ability was as described in U.S.Pat. No. 4,387,244. A 0.15 to 0.25 gram sample of the Mannichcondensation product is placed into an 8 dram vial to which is added 15milliliters toluene and shaken to homogeneity. Next 15 milliliters 00.05 molar solution of FeCl₃ in water is added to the vial and the vialis mechanically shaken for one hour. The contents of the vial areallowed to separate and the toluene layer changes color from yellow topurple, as evidence of iron being chelated, in the presence of theMannich condensation product sequestering agents of the presentinvention.

The term “hydroxyl number” as used herein refers to the amount ofpotassium hydroxide required to neutralize the polyisobutyl-substitutedphenol per gram of sample (milligrams KOH per gram sample).

The term “inert stable oleophilic organic solvent” as used herein refersto solvents that dissolve in gasoline or diesel fuel. Preferably theinert stable oleophilic organic solvent is an aliphatic or an aromatichydrocarbon solvent, such as benzene, toluene, xylene or higher-boilingaromatics or aromatic thinners. Aliphatic alcohols having from about 3carbon atoms to about 8 carbon atoms may also be used in combinationwith the hydrocarbon solvents. Aliphatic alcohols contemplated for usein the present invention are isopropanol, isobutylcarbinol, n-butanoland the like.

The term “Mannich condensation product” as used herein refers to amixture of products obtained by the condensation of apolyisobutyl-substituted hydroxyaromatic compound with an aldehyde andan amino acid, such as, glycine, to form condensation products havingthe formulas given below. The formulas given below are provided only assome examples of the Mannich condensation products believed to be of thepresent invention and are not intended to exclude other possible Mannichcondensation products that may be formed using the methods of thepresent invention.

-   -   wherein R, R₁, X and W are as defined above.

The Mannich condensation products shown above may react further with analdehyde and an amino acid to form larger oligomers.

Preferably the R₁ polyisobutyl group is derived from polyisobutenecontaining at least 70 weight percent methylvinylidene isomer and morepreferably the R₁ polyisobutyl group is derived from polyisobutenecontaining at least 90 weight percent methylvinylidene isomer.

In a preferred embodiment of the Mannich condensation products R is CH₂,R₁ is derived from polyisobutene containing at least 50 weight percentmethylvinylidene isomer and has a number average molecular weight ofabout 700 to about 1300, W is CH₂, and X is a sodium ion.

The term “oil of lubricating viscosity” as used herein refers tolubricating oils which may be mineral oil or synthetic oils oflubricating viscosity and preferably useful in the crankcase of aninternal combustion engine. Crankcase lubricating oils ordinarily have aviscosity of about 1300 centistokes at −17.8° C. to 22.7 centistokes at98.9° C. The lubricating oils may be derived from synthetic or naturalsources. Mineral oil for use as the base oil in this invention includesparaffinic, naphthenic and other oils that are ordinarily used inlubricating oil compositions. Synthetic oils include hydrocarbonsynthetic oils, synthetic esters and Fischer-Tropsch derived base oil.Useful synthetic hydrocarbon oils include liquid polymers ofalpha-olefins having the proper viscosity. Especially useful are thehydrogenated liquid oligomers of C₆ to C₁₂ alpha-olefins such as1-decene trimer. Similarly, alkyl benzenes of proper viscosity, such asdidodecyl benzene, may be used. Useful synthetic esters include theesters of both mono-carboxylic acids and polycarboxylic acids as well asmono-hydroxy alkanols and polyols. Typical examples are didodecyladipate, pentaerthritol tetracapoate, di-2-ethylhexyl adipate,di-laurylsebacate and the like. Complex esters prepared from mixtures ofmono- and di-carboxylic acid and mono- and di-hydroxy alkanols can alsobe used. Blends of hydrocarbon oils and synthetic oils may also be used.For example, blends of 10 weight percent to 25 weight percenthydrogenated 1-decene trimer with 75 weight percent to 90 weight percent683 centistokes at 37.8° C. mineral oil gives an excellent oil base.

The term “polyisobutyl or polyisobutyl substituent” as used hereinrefers to the polyisobutyl substituent on the hydroxyaromatic ring. Thepolyisobutyl substituent has a number average molecular weight in therange of about 400 to about 5,000. Preferably the polyisobutyl moietyhas a number average molecular weight in the range of about 500 to about2,500. More preferably the polyisobutyl moiety has a number averagemolecular weight in the range of about 700 to about 1,500, and mostpreferably the polyisobutyl moiety has a number average molecular weightin the range of about 700 to about 1,100.

Preferably the attachment of the polyisobutyl substituent to thehydroxyaromatic ring is para to the hydroxyl moiety in at least 60percent of the total polyisobutyl-substituted phenol molecules, morepreferably the attachment of the polyisobutyl substituent to thehydroxyaromatic ring is para to the hydroxyl moiety in at least 80percent of the total polyisobutyl-substituted phenol molecules, and mostpreferably the attachment of the polyisobutyl substituent to thehydroxyaromatic ring is para to the hydroxyl moiety on the phenol ringin at least 90 percent of the total polyisobutyl-substituted phenolmolecules.

The term “polyisobutyl-substituted phenol” as used herein refers to apolyisobutyl-substituted phenol ring. The polyisobutyl-substitutedphenol is derived from polyisobutene containing at least 50 weightpercent methylvinylidene isomer. Preferably the polyisobutyl-substitutedphenol is derived from polyisobutene containing at least about 70 weightpercent methylvinylidene isomer and more preferably thepolyisobutyl-substituted phenol is derived from polyisobutene containingat least about 90 weight percent methylvinylidene isomer.

The term “sequestering agent(s)” as used herein refers to compounds thathold a metal atom between two or more atoms of a single molecule of thecompound, thereby neutralizing or controlling harmful metal ions, suchas Fe⁺³, in a lubricating oil or fuel.

The term “VW TDI-1 and VW TDI-2 engine tests” as used herein refers tothe engine test procedures CEC L-78-T-97 and CEC L-78-T-99 respectively,published by the Coordinating European Council (CEC) for the Developmentof Performance Tests for Transportation Fuels, Lubricants and OtherFluids.

Unless otherwise specified, all percentages are in weight percent andthe pressure is atmospheric pressure.

The Mannich Condensation Product

In its broadest aspects the present invention is directed to a Mannichcondensation product prepared by the Mannich condensation of apolyisobutyl-substituted hydroxyaromatic compound, wherein thepolyisobutyl group has number average molecular weight in the range offrom about 400 to about 5,000, an aldehyde, an amino acid or esterderivative thereof, and an alkali metal base.

General Procedure for Preparation of Mannich Condensation ProductSequestering Agents

The Mannich condensation products of this invention are prepared bycombining under reaction conditions a polyisobutyl-substitutedhydroxyaromatic compound, wherein the polyisobutyl group has a numberaverage molecular weight in the range of from about 400 to about 5,000,an aldehyde, an amino acid or ester derivative thereof, and an alkalimetal base. The reaction can be carried out batch wise, or in continuousor semi-continuous mode.

Normally the pressure for this reaction is atmospheric, but the reactionmay be carried out under sub atmospheric or super atmospheric pressureif desired.

The temperature for this reaction may vary widely. The temperature rangefor this reaction can vary from 10° C. to about 200° C., preferably fromabout 50° C. to about 150° C., more preferably from about 70° C. toabout 130° C.

The reaction may be carried out in the presence of a diluent or amixture of diluents. It is important to ensure that the reactants comeinto intimate contact with each other in order for them to react. Thisis an important consideration because the starting materials for theMannich condensation products of the present invention include therelatively non polar polyisobutyl-substituted hydroxyl aromaticcompounds and the relatively polar amino acid or ester derivativethereof. It is therefore necessary to find a suitable set of reactionconditions or diluents that will dissolve all the starting materials.diluents for this reaction must be capable of dissolving the startingmaterials of this reaction and allowing the reacting materials to comein contact with each other. Mixtures of diluents can be used for thisreaction. Useful diluents for this reaction include water, alcohols,(including methanol, ethanol, isopropanol, 1-propanol, 1-butanol,isobutanol, sec-butanol, butanediol, 2-ethylhexanol, 1-pentanol,1-hexanol, ethylene glycol, and the like), DMSO, NMP, HMPA, cellosolve,diglyme, various ethers (including diethyl ether, THF, diphenylether,dioxane, and the like), aromatic diluents (including toluene, benzene,o-xylene, m-xylene, p-xylene, mesitylene and the like), esters, alkanes(including pentane, hexane, heptane, octane, and the like), and variousnatural and synthetic diluent oils (including 100 neutral oils, 150neutral oils, polyalphaolefins, Fischer-Tropsch derived base oil and thelike, and mixtures of these diluents. Mixtures of diluents that form twophases such as methanol and heptane are suitable diluents for thisreaction.

The reaction may be carried out by first reacting the hydroxyaromaticcompound with the alkali metal base, followed by the addition of theamino acid or ester derivative thereof and the aldehyde, or the aminoacid or ester derivative thereof may be reacted with the aldehydefollowed by the addition of the hydroxyaromatic compound and the alkalimetal base, etc.

It is believed that the reaction of the amino acid, such as glycine, orester derivative thereof, plus the aldehyde, such as formaldehyde, mayproduce the intermediate formula

which may ultimately form the cyclic formula

It is believed that these intermediates may react with thehydroxyaromatic compound and the base to form the Mannich condensationproducts of the present invention.

Alternatively, it is believed that the reaction of the hydroxyaromaticcompound with the aldehyde may produce the intermediate formula

It is also believed that this intermediate may react with the amino acidor ester derivative thereof and the base to form the Mannichcondensation product of the present invention.

The time of the reaction can vary widely depending on the temperature.The reaction time can vary between 0.1 hour to about 20 hours,preferably from about 2 hours to about 10 hours, more preferably fromabout 3 hours to about 7 hours.

The charge mole ratio (CMR) of the reagents can also vary over a widerange. Table I below gives a listing of the different formulae that canarise if different charge mole ratios are used. At a minimum theoil-soluble Mannich condensation products that sequester Fe⁺³ shouldpreferable contain at least one polyisobutyl-substituted phenol ring andone amino acid group connected by one aldehyde group and one alkalimetal. The polyisobutyl-substituted phenol/aldehyde/amino acid/basecharge mole ratio for this molecule, also shown in Table I below, is1.0:1.0:1.0:1.0. Other charge mole ratios are possible and the use ofother charge mole ratios can lead to the production of differentmolecules of different formulas.

TABLE I Polyisobutyl-substituted phenol:aldehyde:amino acid:base Product(CMR)

1.0:1.0:1.0:10

1.0:2.0:2.0:2.0

2.0:2.0:1.0:1.0

2.0:3.0:2.0:2:0

3.0:4.0:2.0:2.0

All these products arising from other charge mole ratios may all bepresent alone, as a single component, or as combinations of severalcomponents in a complex mixture of products.

In the broadest sense the polyisobutyl-substituted phenol: aldehyde:amino acid: base CMR can vary from 1.0 to 20.0:1.0 to 39.0:1.0 to20.0:1.0 to 4.0. Preferably the polyisobutyl-substituted phenol:aldehyde: amino acid: base CMR can vary from 1.0 to 5.0:1.0 to 10.0:1.0to 6.0:1.0 to 3.0. More preferably the polyisobutyl-substituted phenol:aldehyde: amino acid: base CMR can vary from 1.0 to 3.0:1.0 to 5.0:1.0to 3.0:1.0 to 2.0. Most preferably the polyisobutyl-substituted phenol:amino acid: aldehyde: base CMR is 1:1:2:1.

Compounds suitable for use in the preparation of the Mannichcondensation products of the present invention are given below:

Polyisobutyl-Substituted Hydroxyaromatic Compound

A variety of polyisobutyl-substituted hydroxyaromatic compounds can beutilized in the preparation of the Mannich condensation products of thisinvention. The critical feature is that the polyisobutyl substituent belarge enough to impart oil solubility to the finished Mannichcondensation product. In general the number of carbon atoms on thepolyisobutyl substituent group that are required to allow for oilsolubility of the Mannich condensation product is on the order of aboutC₂₀ and higher. This corresponds to a molecular weight in the range ofabout 400 to about 5,000. It is desirable that the C₂₀ or higher alkylsubstituent on the phenol ring be located in the position para to the OHgroup on the phenol.

In general, one unsubstituted carbon atom in the ortho position to thehydroxyl group on the aromatic ring is required in order to prepare theMannich condensation products of this invention. For example, phenolsubstituted in the para position with a polyisobutyl substituent thatcontains 20 or more carbon atoms is a preferred polyisobutyl-substitutedphenol raw material for this invention.

Di-substituted phenols are also suitable starting materials for theMannich condensation products of this invention. Di-substituted phenolsare suitable provided that they are substituted in such a way that thereis an unsubstituted ortho position on the phenol ring. Examples ofsuitable di-substituted phenols are o-cresol derivatives substituted inthe para position with a C₂₀ or greater polyisobutyl substituent and thelike.

A preferred polyisobutyl-substituted phenol has the following formula:

wherein R1 is polyisobutyl group derived from polyisobutene containingat least 50 weight percent methylvinylidene isomer and having a numberaverage molecular weight in the range of about 400 to about 5,000, and Yis hydrogen.

In the above process the polyisobutyl substituent on thepolyisobutyl-substituted phenol has a number average molecular weight inthe range of about 400 to about 5,000. Preferably the polyisobutylsubstituent on the polyisobutyl-substituted phenol has a number averagemolecular weight of about 500 to about 2,5000. More preferably thepolyisobutyl substituent on the polyisobutyl-substituted phenol has anumber average molecular weight of about 700 to about 1,500. Mostpreferably the polyisobutyl substituent on the polyisobutyl-substitutedphenol has a number average molecular weight of about 700 to about1,100.

The polyisobutyl-substituted phenol in the above process is preferablyderived from polyisobutene containing at least about 50 weight percentmethylvinylidene isomer. More preferably the polyisobutyl-substitutedphenol is derived from polyisobutene containing at least about 70 weightpercent methylvinylidene isomer and most preferably thepolyisobutyl-substituted phenol is derived from polyisobutene containingat least about 90 weight percent methylvinylidene isomer.

Suitable polyisobutenes may be prepared using boron trifluoride (BF₃)alkylation catalyst as described in U.S. Pat. Nos. 4,152,499 and4,605,808.

Commercially available polyisobutenes having a high alkylvinylidenecontent include Glissopal® 1000, 1300 and 2300, available from BASF.

The preferred polyisobutyl-substituted phenol for use in the preparationof the Mannich condensation products of the present invention is amono-substituted phenol, wherein the polyisobutyl substituent isattached at the para-position to the phenol ring. However, otherpolyisobutyl-substituted phenols that may undergo the Mannichcondensation reaction may also be used for preparation of the Mannichcondensation products of the present invention.

Solvent

Solvents may be employed to facilitate handling and reaction of thepolyisobutyl-substituted phenols in the preparation of the Mannichcondensation products of the present invention. Examples of suitablesolvents are hydrocarbon compounds such as heptane, benzene, toluene,chlorobenzene, aromatic solvent, neutral oil of lubricating viscosity,paraffins and naphthenes. Examples of other commercially availablesuitable solvents that are aromatic mixtures include Chevron® Aromatic100N, neutral oil, Exxon® 150N, neutral oil.

If the Mannich condensation product sequestering agent prepared by theabove process is to be used as an additive in lubricating oil, then thepolyisobutyl-substituted phenol may be first dissolved in analkyl-substituted aromatic solvent. Preferably the alkyl substituent onthe aromatic solvent has from about 3 carbon atoms to about 15 carbonatoms. More preferably the alkyl substituent on the aromatic solvent hasfrom about 6 carbon atoms to about 12 carbon atoms.

Base

Typical bases include alkali metal hydroxides and alkali metalalkoxides. Preferably the base is an alkali metal hydroxide selectedfrom the group consisting of sodium hydroxide, lithium hydroxide orpotassium hydroxide. More preferably the alkali metal hydroxide issodium hydroxide or potassium hydroxide. Most preferably the base issodium hydroxide. If the Mannich condensation product sequestering agentis to be used as a fuel additive it may be desirable to replace thealkali metal ion on the Mannich condensation products with an ammoniumion. For other uses the alkali metal ion on the Mannich condensationproducts may also be replaced with Group II metals of the PeriodicTable.

Aldehyde

Aldehydes contemplated for use in the process of the present inventionare formaldehyde or aldehydes having the formula

-   -   wherein R′ is branched or linear alkyl, having from one carbon        atom to about 10 carbon atoms, cycloalkyl having from about 3        carbon atoms to about 10 carbon atoms, aryl having from about 6        carbon atoms to about 10 carbon atoms, alkaryl having from about        7 carbon atoms to about 20 carbon atoms, or aralkyl having from        about 7 carbon atoms to about 20 carbon atoms.

Representative aldehydes for use in the preparation of the Mannichcondensation products of the present invention include, but are notlimited to aliphatic aldehydes such as formaldehyde, acetaldehyde,propionaldehyde, butyraldehyde, valeraldehyde, caproaldehyde andheptaldehyde.

Aromatic aldehydes are also contemplated for use in the preparation ofthe Mannich condensation products of the present invention, such asbenzaldehyde, alkylbenzaldehyde and hydroxybenzaldehyde.Para-tolualdehyde is an example of an alkylbenzaldehyde.

Also useful are formaldehyde producing reagents, such asparaformaldehyde and aqueous formaldehyde solutions such as formalin.Aldehydes most preferred for use in the in the preparation of theMannich condensation products of the present invention areparaformaldehyde and formalin.

Aldehydes most preferred for use in the in the preparation of theMannich condensation products of the present invention areparaformaldehyde and formalin.

Preferably the aldehyde is formaldehyde. By formaldehyde is meant allits forms, including gaseous, liquid and solid. Examples of gaseousformaldehyde is the monomer CH₂O and the trimer, (CH₂O)₃ (trioxane)having the formula given below.

Examples of liquid formaldehyde are the following:

-   -   4. Monomer CH₂O in ethyl ether.    -   5. Monomer CH₂O in water which has the formulas CH₂(H₂O)₂        (methylene glycol) and HO(—CH₂O)_(n)—H.    -   6. Monomer CH₂O in methanol which has the formulas OHCH₂OCH₃ and        CH₃O(—CH₂O)_(n)—H.

Formaldehyde solutions are commercially available in water and variousalcohols. In water it is available as a 37%-50% solution. Formalin is a37% solution in water.

Formaldehyde is also commercially available as linear and cyclic(trioxane) polymers. Linear polymers may be low molecular weight or highmolecular weight polymers.

Amino Acid

The amino acid or the ester derivative thereof used in the above processhas the formula

-   -   W is —[CHR″]—_(m) wherein each R″ is independently H, alkyl        having one carbon atom to about 15 carbon atoms, or a        substituted-alkyl having one carbon atom to about 10 carbon        atoms and one or more substituents selected from the group        consisting of amino, amido, benzyl, carboxyl, hydroxyl,        hydroxyphenyl, imidazolyl, imino, phenyl, sulfide, or thiol; and        m is an integer from one to 4 and A is hydrogen or alkyl having        one carbon atoms to about 6 carbon atoms.

Preferably A is hydrogen in the above formula. The preferred alkyl inthe above formula is methyl or ethyl.

Preferably the amino acid is glycine.

Some examples of alpha amino acids contemplated for use in thepreparation of the Mannich condensation products of the presentinvention are given below in Table II.

TABLE II Log Name Formula K^(25°) ^(C., 0 Ionic strength) Alanine

9.87 Arginine

8.99 Asparagine

8.72 * Aspartic Acid

10.0 Cysteine

10.77 Cystine

8.80 ** Glutamic Acid

9.95 Glutamine

9.01* Glycine

9.78 Histidine

9.08* Hydro- xylysine

Isoleucine

9.75 Leucine

9.75 Lysine

10.69* Methionine

9.05 Phenyl- alanine

9.31 Serine

9.21 Threonine

9.10 Tyrosine

10.47 Valine

9.72 *0.1 ionic strength. **20° C. and 0.1 ionic strength.

The present invention is also directed to a lubricating oil additivecomposition comprising a major amount of an oil of lubricating viscosityand a minor amount of the Mannich condensation product sequesteringagent of the present invention. A mixture of Mannich condensationproduct sequestering agents are also contemplated in the lubricating oiladditive composition of the present invention. Typically the lubricatingoil composition will contain Mannich condensation product sequesteringagents of this invention in the range of from about 0.01 weight percentto about 10 weight percent, preferably in the range of from about 0.1weight percent to about 5 weight percent and more preferably in therange of from about 0.3 weight percent to about 2 weight percent. Thelubricating oil additive composition will generally contain otheradditives including detergents (overbased and non-overbased),dispersants, extreme pressure agents, wear inhibitors, rust inhibitors,foam inhibitors, corrosion inhibitors, pour point depressants,antioxidants, zinc di-thiophosphates and a variety of other well knownadditives.

The present invention is also directed to a lubricating oil concentrate.Lubricating oil additive concentrates usually include from 90 weightpercent to 10 weight percent of an organic liquid diluent and from 10weight percent to 90 weight percent (on a dry polymer basis) of theadditive of this invention. Typically, the concentrates containsufficient diluent to make them easy to handle during shipping andstorage. Generally, the lubricating oil concentrate will contain theMannich condensation product sequestering agents of this invention inthe range of from about 10 weight percent to about 90 weight percent drypolymer Mannich condensation product, preferably in the range of fromabout 30 weight percent to about 70 weight percent dry polymer Mannichcondensation product, and more preferably about 50 weight percent drypolymer Mannich condensation product.

The present invention is also directed to a fuel additive compositioncomprising a major amount of hydrocarbons boiling in the gasoline ordiesel range and a minor effective amount of the Mannich condensationproduct sequestering agent of the present invention. A mixture ofMannich condensation product sequestering agents are also contemplatedin the fuel composition of the present invention. Typically the fuelcomposition will contain the Mannich condensation product sequesteringagents of this invention in the range of from about 25 parts per millionto about 2,500 parts per million, preferably in the range of from about50 parts per million to about 1,500 parts per million, and morepreferably in the range of from about 70 parts per million to about1,000 parts per million, The gasoline fuel additive composition of thepresent invention may include other fuel additives, includingoxygenates, anti-knock agents, dispersants, detergents, lead scavengers,anti-oxidants, pour point depressants, corrosion inhibitors anddemulsifiers. The gasoline fuels may also contain amounts of otherfuels, for example, methanol. The diesel fuel additive composition ofthe present invention may also contain other additives, including pourpoint depressants, flow improvers and cetane improvers. The diesel fuelsmay also contain amounts of other fuels, for example, methanol.

A further embodiment of the present invention is also directed to a fuelconcentrate comprising an inert stable oleophilic organic solventboiling in the range of from about 65° C. to about 204° C. and fromabout 10 weight percent to about 90 weight percent of one or moreMannich condensation product sequestering agents of the presentinvention. Generally the fuel concentrate will contain Mannichcondensation product sequestering agents of the present invention in therange of from about 10 weight percent to about 70 weight percent,preferably in the range of from about 10 weight percent to about 50weight percent and more preferably in the range of from about 20 weightpercent to about 40 weight percent.

A fuel-soluble, non-volatile carrier fluid or oil may also be used withthe fuel additive composition of this invention. The carrier fluid is achemically inert hydrocarbon-soluble liquid vehicle which substantiallyincreases the non-volatile residue, or the solvent-free liquid fractionof the fuel additive composition while not overwhelmingly contributingto octane requirement increase. The carrier fluid may be a natural or asynthetic oil, such as mineral oil or refined petroleum oils.

Typically, an engine lubricating oil composition may contain thefollowing components:

-   -   (a) A major amount of oil of lubricating viscosity;    -   (b) 0.01 weight percent to 10.0 weight percent of at least one        Mannich condensation product of the present invention;    -   (c) 1.0 weight percent to 10.0 weight percent of at least one        borated or non-borated succinimide ashless detergent;    -   (d) 0.05 weight percent to 0.5 weight percent, as calcium, of at        least one calcium sulfonate, phenate or salicylate detergent;    -   (e) 0.02 weight percent to 0.2 weight percent, as phosphorus, of        at least one secondary or mixture of primary and secondary alkyl        zinc dithiophosphate;    -   (f) 0.0 weight percent to 5.0 weight percent of at least one        diphenyl amine oxidation inhibitor;    -   (g) 0.0 weight percent to 0.5 weight percent of, as molybdenum,        of at least one molybdenum succinimide oxidation inhibitor;    -   (h) 0.0 weight percent to 5.0 weight percent of at least one        partial; carboxylic ester or borated ester friction modifier;    -   (i) 0.0 weight percent to 0.05 weight percent of at least one        supplemental anti-wear/extreme pressure agent, such as        molybdenum dithiocarbamate;    -   (j) 0.0 weight percent to 0.1 weight percent of at least one        foam inhibitor; and    -   (k) 0.0 weight percent to 2.0 weight percent of at least one        olefin copolymer viscosity index improver.

The Mannich condensation products of the present invention may also beemployed as dispersants in lubricating oil. For use as dispersants infuels the alkali metal ions in Mannich condensation products arereplaced with ammonium ions.

EXAMPLES Example 1 Preparation of Mannich Condensation Product Using1,000 Molecular Weight Polyisobutyl-Substituted Phenol

To a 1.0 liter three-neck flask equipped with a temperature probe,mechanical stirrer and reflux condenser were added 4.0 grams of sodiumhydroxide in 3.0 milliliters of water (0.1 moles), 300 milliliters ofmethanol (boiling point 65° C.), 7.5 grams (0.1 moles) of glycine and6.59 grams (0.2 moles) of paraformaldehyde. The reaction mixture wasgently warmed (40° C.) for 30 minutes. To this was added, at a refluxtemperature, 134.8 grams (0.1 moles) of 1,000 molecular weightpolyisobutyl-substituted phenol, prepared as described in U.S. Pat. Nos.5,300,701 and 6,274,777, (hydroxyl number 41.6 milligrams KOH per gramsample) diluted in C₉ aromatic solvent The reaction mixture was heatedat reflux temperature for 17 hours. Next the methanol was removed undervacuum and the product obtained.

This product was soluble in diluent oil. The product had a viscosity of1,653 centistokes at 100° C.

Comparative Example A Preparation of Mannich Condensation Product UsingC₁₂ Alkyl Substituted Phenol

To a 2.0 liter three-neck flask equipped with a temperature probe,mechanical stirrer and reflux condenser were added 40 grams of sodiumhydroxide in 20 milliliters of water (0.1 moles) and 700 milliliters ofmethanol (boiling point 65° C.). The reaction mixture was heated gently(40° C.) for 15 minutes to dissolve the sodium hydroxide. To thereaction mixture was added 75.07 grams (1.0 mole) of glycine and 60.06grams (2.0 moles) of paraformaldehyde with gentle heating (40° C.). Tothis was added 286.29 grams (0.1 moles) of C₁₂ propylene tetramersubstituted phenol, OLOA 200® (hydroxyl number 196 milligrams KOH pergram sample), available from Chevron Oronite Company LLC. The reactionmixture was heated at reflux temperature for 17 hours. Next the methanolwas removed under vacuum. The product obtained was dissolved in toluene.The product had to be dissolved in toluene because it was only slightlysoluble in hexane. The product was filtered through Celite® and thesolvent (toluene) removed under vacuum and the product was obtained.

Comparative Example B Solubility of Mannich Condensation ProductPrepared from C₉ Alkyl Substituted Phenol

Mannich condensation product, 15.1 grams, was prepared from C₉alkyl-substituted phenol as described in U.S. Pat. No. 4,387,244. Theproduct was dissolved in 50 milliliters toluene at elevated temperature(100° C.). To this was added 35 grams Citcon® 100N, neutral diluent oil.Next most of the toluene was removed under vacuum. A total of 52 gramsof product (30 product and 70 percent diluent oil) was obtained. Theproduct was cloudy indicating that Mannich condensation product waspoorly soluble in diluent oil.

Example 2 High Temperature PCDO Performance VW TDI-1 Engine Test Using10w40 Oil

The performance of a sample of the Mannich condensation product preparedin Example 1 was evaluated in a VW TD-1 Engine Test and compared to afully formulated oil without the Mannich condensation product. Theproduct prepared in Example 1 was added at a 1.0 percent treat rate to afully formulated oil containing typical amounts of ashless dispersant,phenate, overbased sulfonate, LOB sulfonate zinc di-thiophosphate, wearinhibitors, etc., in a SAE grade 10w40, partial synthetic oil. Theresults of the VW TDI-1 Engine Test are summarized below in Table II.The data show that the oil containing the Mannich condensation productof the present invention had significantly better performance that thebaseline oil. The baseline oil ran for only 42 hours and was terminatedearly. The average piston merit was 60.6, and the average ring stickingwas 2.0. This was a failing engine test. The oil containing the Mannichcondensation product of the present invention completed the 60 hour testand gave average piston merit of 66.7, and average ring sticking of0.63. This was a passing engine test result. It is believed that the oilcontaining the Mannich condensation product of the present inventionperformed better than the baseline oil alone because of the Mannichcondensation product's ability to sequester metal ions, thus preventingmetal ion catalyzed oxidation and polymerization reactions fromoccurring.

TABLE II Average Piston Average Ring Example Test Hours Merit StickingBaseline 42 60.6 2.00 Example 2 60 66.7 0.63

Example 3 High Temperature PCDO Performance VW TDI-2 Engine Test Using5w30 Oil

The performance of a sample of the Mannich condensation product,prepared in Example 1 dissolved at 1.0 percent level in a fullyformulated Group III 5w30 baseline oil, was determined in a VW TD-2Engine Test. This was compared to the baseline oil without the Mannichcondensation product. The results of the VW TDI Engine Test aresummarized below in Table III. The data show that the oil containing theMannich condensation product of the present invention had significantlybetter performance than the baseline. The oil containing the Mannichcondensation product of the present invention performed better foraverage piston cleanliness and there was no ring sticking. It isbelieved that the Mannich condensation product of the present inventionperformed better than the Group III Base Oil alone because of theproduct's ability to sequester metal ions, thus preventing metal ioncatalyzed oxidation and polymerization reactions in the hydrocarbon baseoil.

TABLE III Average Piston Average Ring Example Test Hours Merit StickingBaseline 54 55 none Example 3 54 60 none

Example 4 High Temperature PCDO Performance VW TDI-2 Engine Test Using10w40 Oil

The performance of a sample of the Mannich condensation product,prepared in Example 1 dissolved at 1.0 percent level in a fullyformulated 5w40 baseline oil, was measured in a VW TD-2 Engine Test.This was compared to the baseline oil without the Mannich condensationproduct. The results of the VW TDI Engine Test are summarized below inTable IV. The data show that the oil containing the Mannich condensationproduct of the present invention had significantly better performancethan the baseline. The oil containing the Mannich condensation productof the present invention performed better for, average piston merit andaverage ring sticking, than the baseline. It is believed that the oilcontaining the Mannich condensation product of the present inventionperformed better than the baseline because of the product's ability tosequester metal ions, thus preventing metal ion catalyzed oxidation andpolymerization reactions in the hydrocarbon base oil.

TABLE IV Average Piston Average Ring Example Test Hours Merit StickingBaseline 54 42 1.875 Example 4 54 54.8 0.625

Example 5 Preparation of Mannich Condensation Product Using 550Molecular Weight Polyisobutyl-Substituted Phenol

To a 2 liter 3 neck glass round bottom flask equipped with a refluxcondenser, nitrogen inlet, mechanical stirrer, heating mantle, andthermocouple, was added NaOH, 8.00 grams (50 percent agueous solution),(0.10 moles) and 300 milliliters methanol. This was stirred and heatedto about 50° C. for 15 minutes. To this was added glycine, 7.51 grams(0.100 moles) and paraformaldehyde, 6.59 grams 0.220 moles. The solutionwas then heated to reflux and to this was added 66.50 grams (0.101moles) polyisobutyl-substituted phenol (prepared using the proceduredescribed in U.S. Pat. Nos. 5,300,701 and 6,274,777 using Glissopal®,M_(n)=550, methylvinylidene content greater than 50 weight percent).This was heated at reflux for 20 hours. The resulting oil and methanolphases were dissolved in hexane, filtered through Celite® 521, anddiluted with toluene. The solvent was then removed in vacuo to yield aglassy yellow solid, melting point 110° C.

This example shows that 550 molecular weight polyisobutyl-substitutedphenol can also be used to make the Mannich condensation products ofthis invention.

1. A Mannich condensation product prepared by the Mannich condensationof: (a) a polyisobutyl-substituted hydroxyaromatic compound, wherein thepolyisobutyl group is derived from polyisobutene containing at least 50weight percent methylvinylidene isomer and has a number averagemolecular weight in the range of from about 400 to about 5,000; (b) analdehyde; (c) an amino acid or ester derivative thereof; and (d) analkali metal base.
 2. The Mannich condensation product of claim 1,wherein the polyisobutyl group of the polyisobutyl-substitutedhydroxyaromatic compound in (a) is derived from polyisobutene containingat least 70 weight percent methylvinylidene isomer.
 3. The Mannichcondensation product of claim 2, wherein the polyisobutyl group isderived from polyisobutene containing at least 90 weight percentmethylvinylidene isomer.
 4. The Mannich condensation product of claim 1,wherein the polyisobutyl group has a number average molecular weight inthe range of from about 500 to about 2,500.
 5. The Mannich condensationproduct of claim 4, wherein the polyisobutyl group has a number averagemolecular weight in the range of from about 700 to about 1,500.
 6. TheMannich condensation product of claim 5, wherein the polyisobutyl grouphas a number average molecular weight in the range of from about 700 toabout 1,100.
 7. The Mannich condensation product of claim 1, wherein thealdehyde is formaldehyde or paraformaldehyde.
 8. The Mannichcondensation product of claim 7, wherein the aldehyde isparaformaldehyde.
 9. The Mannich condensation product of claim 1,wherein the polyisobutyl-substituted hydroxyaromatic compound is presentin a diluent.
 10. The Mannich condensation product of claim 9, whereinthe diluent is an alkanol having one carbon atom to about 10 carbonatoms.
 11. The Mannich condensation product of claim 10, wherein thealkanol is methanol.
 12. The Mannich condensation product of claim 1,wherein the base is an alkali metal hydroxide.
 13. The Mannichcondensation product of claim 12, wherein the alkali metal hydroxide issodium hydroxide.
 14. The Mannich condensation product of claim 1,wherein the amino acid is glycine.
 15. A Mannich condensation productprepared by the Mannich condensation of: (a) a polyisobutyl-substitutedhydroxyaromatic compound having the formula

wherein R₁ is polyisobutyl derived from polyisobutene containing atleast 50 weight percent methylvinylidene isomer and having a numberaverage molecular weight in the range of about 400 to about 5,000, R₂ ishydrogen or lower alky having one carbon atom to about 10 carbon atoms,and R₃ is hydrogen or —OH; (b) a formaldehyde or an aldehyde having theformula

wherein R′ is branched or linear alkyl having one carbon atom to about10 carbon atoms, cycloalkyl having from about 3 carbon atoms to about 10carbon atoms, aryl having from about 6 carbon atoms to about 10 carbonatoms, alkaryl having from about 7 carbon atoms to about 20 carbonatoms, or aralkyl having from about 7 carbon atoms to about 20 carbonatoms; (c) an amino acid or ester derivative thereof having the formula

wherein W is —[CHR″]—_(m) wherein each R″ is independently H, alkylhaving one carbon atom to about 15 carbon atoms, or a substituted-alkylhaving one carbon atom to about 10 carbon atoms and one or moresubstituents selected from the group consisting of amino, amido, benzyl,carboxyl, hydroxyl, hydroxyphenyl, imidazolyl, imino, phenyl, sulfide,or thiol; and m is an integer from one to 4, A is hydrogen or alkylhaving one carbon atom to about 6 carbon atoms; and (d) an alkali metalbase.
 16. A Mannich condensation product having the formula

wherein each R is independently —CHR′—, wherein R′ is branched or linearalkyl having one to about 10 carbon atoms, cycloalkyl having from about3 carbon atoms to about 10 carbon atoms, aryl having from about 6 carbonatoms to about 10 carbon atoms, alkaryl having from about 7 carbon atomsto about 20 carbon atoms, or aralkyl having from about 7 carbon atoms toabout 20 carbon atoms, R₁ is a polyisobutyl group derived frompolyisobutene containing at least 50 weight percent methylvinylideneisomer and having a number average molecular weight in the range ofabout 400 to about 5,000; X is hydrogen, an alkali metal ion, or alkylhaving one carbon atom to about 6 carbon atoms; W is —[CHR″]—, whereineach R″ is independently H, alkyl having one carbon atom to about 15carbon atoms, or a substituted-alkyl having one carbon atom to about 10carbon atoms and one or more substituents selected from the groupconsisting of amino, amido, benzyl, carboxyl, hydroxyl, hydroxyphenyl,imidazolyl, imino, phenyl, sulfide, or thiol; and m is an integer fromone to 4; Y is hydrogen, alkyl having one carbon atom to about 10 carbonatoms, —CHR′OH, wherein R′ is as defined above, or

wherein Y′ is —CHR′OH, wherein R′ is as defined above; and R, X, and Ware as defined above; Z is hydroxyl, a hydroxyphenyl group of theformula

wherein R, R₁, Y′, X, and W are as defined above, and n is an integerfrom 0 to 20, with the proviso that when n=0, Z must be:

wherein R, R₁, Y′, X, and W are as defined above.
 17. The Mannichcondensation product of claim 16, wherein the polyisobutyl group of thepolyisobutyl-substituted hydroxyaromatic compound in (a) is derived frompolyisobutene containing at least 70 weight percent methylvinylideneisomer.
 18. The Mannich condensation product of claim 17, wherein thepolyisobutyl group is derived from polyisobutene containing at least 90weight percent methylvinylidene isomer.
 19. The Mannich condensationproduct of claim 16, wherein R₁ is a polyisobutyl group having a numberaverage molecular weight of about 500 to about 2,500.
 20. The Mannichcondensation product of claim 19, wherein R₁ is a polyisobutyl grouphaving a number average molecular weight of about 700 to about 1,500.21. The Mannich condensation product of claim 20, wherein R₁ is apolyisobutyl group having a number average molecular weight of about 700to about 1,100.
 22. A method for preventing metal ion catalyzedoxidation and polymerization reactions in a hydrocarbon mediumcomprising sequestering the metal ion by the addition of an effectiveamount of a compound having the formula

wherein each R is independently —CHR′—, wherein R′ is branched or linearalkyl having one to about 10 carbon atoms, cycloalkyl having from about3 carbon atoms to about 10 carbon atoms, aryl having from about 6 carbonatoms to about 10 carbon atoms, alkaryl having from about 7 carbon atomsto about 20 carbon atoms, or aralkyl having from about 7 carbon atoms toabout 20 carbon atoms R₁ is a polyisobutyl group derived frompolyisobutene containing at least 50 weight percent methylvinylideneisomer and having a number average molecular weight in the range ofabout 400 to about 5,000; X is hydrogen, an alkali metal ion, or alkylhaving one carbon atom to about 6 carbon atoms; W is —[CHR″]—_(m)wherein each R″ is independently H, alkyl having one carbon atom toabout 15 carbon atoms, or a substituted-alkyl having one carbon atom toabout 10 carbon atoms and one or more substituents selected from thegroup consisting of amino, amido, benzyl, carboxyl, hydroxyl,hydroxyphenyl, imidazolyl, imino, phenyl, sulfide, or thiol; and m is aninteger from one to 4; Y is hydrogen, alkyl having one carbon atom toabout 10 carbon atoms, —CHR′OH, wherein R′ is as defined above, or

wherein Y′ is —CHR′OH, wherein R′ is as defined above; and R, X, and Ware as defined above; Z is hydroxyl, a hydroxyphenyl group of theformula

wherein R, R₁, Y′, X, and W are as defined above, and n is an integerfrom 0 to 20, with the proviso that when n=0, Z must be

wherein R, R₁, Y′, X, and W are as defined above.
 23. The method ofclaim 22, wherein R is CH₂, R₁ is a polyisobutyl group derived frompolyisobutene containing at least 50 weight percent methylvinylideneisomer and having a number average molecular weight of about 700 toabout 1,100, W is CH₂, X is a sodium ion and n is an integer between 0and
 20. 24. A method for preventing metal ion catalyzed oxidation andpolymerization reactions in a hydrocarbon medium comprising sequesteringthe metal ion by the addition of an effective amount of the Mannichcondensation product of claim
 15. 25. A process for preparing a Mannichcondensation product comprising: mixing under reaction conditions, (a) apolyisobutyl-substituted hydroxyaromatic compound having the formula

wherein R₁ is polyisobutyl derived from polyisobutene containing atleast 50 weight percent methylvinylidene isomer and a number averagemolecular weight in the range of about 400 to about 5,000, R₂ ishydrogen or lower alky having one carbon atom to about 10 carbon atoms,and R₃ is hydrogen or —OH; (b) a formaldehyde or an aldehyde having theformula

or polymers thereof, wherein R′ is branched or linear alkyl having onecarbon atom to about 10 carbon atoms, cycloalkyl having from about 3carbon atoms to about 10 carbon atoms, aryl having from about 6 carbonatoms to about 10 carbon atoms, alkaryl having from about 7 carbon atomsto about 20 carbon atoms, or aralkyl having from about 7 carbon atoms toabout 20 carbon atoms; (c) an amino acid or ester derivative thereofhaving the formula

wherein W is —[CHR″]—_(m) wherein each R″ is independently H, alkylhaving one carbon atom to about 15 carbon atoms, or a substituted-alkylhaving one carbon atom to about 10 carbon atoms and one or moresubstituents selected from the group consisting of amino, amido, benzyl,carboxyl, hydroxyl, hydroxyphenyl, imidazolyl, imino, phenyl, sulfide,or thiol; and m is an integer from one to 4, A is hydrogen or alkylhaving one carbon atom to about 6 carbon atoms; (d) in the presence ofan alkali metal base to obtain the Mannich condensation product.
 26. Theprocess of claim 25, wherein the polyisobutyl group of thepolyisobutyl-substituted hydroxyaromatic compound in (a) is derived frompolyisobutene containing at least 70 weight percent methylvinylideneisomer.
 27. The process of claim 26, wherein the polyisobutyl group isderived from polyisobutene containing at least 90 weight percentmethylvinylidene isomer.
 28. The process of claim 25, wherein the R₁polyisobutyl in (a) has a number average molecular weight of about 500to about 2,500.
 29. The process of claim 28, wherein the R₁ polyisobutylin (a) has a number average molecular weight of about 700 to about1,500.
 30. The process of claim 29, wherein the R₁ polyisobutyl in (a)has a number average molecular weight of about 700 to about 1,100. 31.The process of claim 25, wherein the aldehyde (b) is formaldehyde orparaformaldehyde.
 32. The process of claim 31, wherein the aldehyde isparaformaldehyde.
 33. The process of claim 25, wherein thepolyisobutyl-substituted hydroxyaromatic compound (a) is in a diluent.34. The process of claim 33, wherein the diluent is an alkanol havingone carbon atom to about 10 carbon atoms.
 35. The process of claim 34,wherein the alkanol is methanol.
 36. The process of claim 25, whereinthe base in (d) is an alkali metal hydroxide.
 37. The process of claim36, wherein the alkali metal hydroxide is sodium hydroxide.
 38. Theprocess of claim 25, wherein the amino acid (c) is glycine.
 39. Alubricating oil composition comprising a major amount of an oil oflubricating viscosity and a minor effective amount of one or moreMannich condensation products having the formula

wherein each R is independently —CHR′—, wherein R′ is branched or linearalkyl having one to about 10 carbon atoms, cycloalkyl having from about3 carbon atoms to about 10 carbon atoms, aryl having from about 6 carbonatoms to about 10 carbon atoms, alkaryl having from about 7 carbon atomsto about 20 carbon atoms, or aralkyl having from about 7 carbon atoms toabout 20 carbon atoms, R₁ is a polyisobutyl group derived frompolyisobutene containing at least 50 weight percent methylvinylideneisomer and having a number average molecular weight in the range ofabout 400 to about 5,000; X is hydrogen, an alkali metal ion, or alkylhaving one carbon atom to about 6 carbon atoms; W is —[CHR″]—_(m)wherein each R″ is independently H, alkyl having one carbon atom toabout 15 carbon atoms, or a substituted-alkyl having one carbon atom toabout 10 carbon atoms and one or more substituents selected from thegroup consisting of amino, amido, benzyl, carboxyl, hydroxyl,hydroxyphenyl, imidazolyl, imino, phenyl, sulfide, or thiol; and m is aninteger from one to 4; Y is hydrogen, alkyl having one carbon atom toabout 10 carbon atoms, —CHR′OH, wherein R′ is as defined above, or

wherein Y′ is —CHR′OH, wherein R′ is as defined above; and R, X, and Ware as defined above; Z is hydroxyl, a hydroxyphenyl group of theformula

wherein R, R₁, Y′, X, and W are as defined above, and n is an integerfrom 0 to 20, with the proviso that when n=0, Z must be

wherein R, R₁, Y′, X, and W are as defined above.
 40. The lubricatingoil composition of claim 39, wherein R is CH₂, R₁ is polyisobutyl groupderived from polyisobutene containing at least 50 weight percentmethylvinylidene isomer and having a number average molecular weight ofabout 700 to about 1,100, W is CHR″, wherein R″ is H, X is a sodium ionand n is an integer between 0 and
 20. 41. A lubricating oil compositioncomprising a major amount of an oil of lubricating viscosity and a minoreffective amount of one or more Mannich condensation products of claim15.
 42. A lubricating oil concentrate comprising from about 90 weightpercent to about 10 weight percent of an oil of lubricating viscosityand from about 10 weight percent to about 90 weight percent of one ormore lubricating Mannich condensation products having the formula

wherein each R is independently —CHR′—, wherein R′ is branched or linearalkyl having one to about 10 carbon atoms, cycloalkyl having from about3 carbon atoms to about 10 carbon atoms, aryl having from about 6 carbonatoms to about 10 carbon atoms, alkaryl having from about 7 carbon atomsto about 20 carbon atoms, or aralkyl having from about 7 carbon atoms toabout 20 carbon atoms, and R₁ is a polyisobutyl group containing atleast 50 weight percent methylvinylidene isomer and having a numberaverage molecular weight in the range of about 400 to about 5,000; X ishydrogen, an alkali metal ion, or alkyl having one to about 6 carbonatoms; W is —[CHR″]—_(m) wherein each R″ is independently H, alkylhaving one carbon atom to about 15 carbon atoms, or a substituted-alkylhaving one carbon atom to about 10 carbon atoms and one or moresubstituents selected from the group consisting of amino, amido, benzyl,carboxyl, hydroxyl, hydroxyphenyl, imidazolyl, imino, phenyl, sulfide,or thiol; and m is an integer from one to 4; Y is hydrogen, alkyl havingone carbon atom to about 10 carbon atoms, —CHR′OH, wherein R′ is asdefined above, or

wherein Y′ is —CHR′OH, wherein R′ is as defined above; and R, X, and Ware as defined above; Z is hydroxyl, a hydroxyphenyl group of theformula

wherein R, R₁, Y′, X, and W are as defined above, and n is an integerfrom 0 to 20, with the proviso that when n=0, Z must be

wherein R, R₁, Y′, X, and W are as defined above.
 43. The lubricatingoil concentrate of claim 42, wherein R is CH₂, R₁ is alkyl group havinga number average molecular weight of about 700 to about 1,000, W isCHR″, wherein R″ is H, X is a sodium ion and n is an integer between 0and
 20. 44. A lubricating oil concentrate comprising from about 90weight percent to about 10 weight percent of an oil of lubricatingviscosity and from about 10 weight percent to about 90 weight percent ofone or more lubricating Mannich condensation products of claim
 15. 45. Afuel composition comprising a major amount of hydrocarbons boiling inthe gasoline or diesel range and a minor effective amount of one or moreMannich condensation products having the formula

wherein each R is independently —CHR′—, wherein R′ is branched or linearalkyl having one to about 10 carbon atoms, cycloalkyl having from about3 carbon atoms to about 10 carbon atoms, aryl having from about 6 carbonatoms to about 10 carbon atoms, alkaryl having from about 7 carbon atomsto about 20 carbon atoms, or aralkyl having from about 7 carbon atoms toabout 20 carbon atoms, and R₁ is a polyisobutyl group containing atleast 50 weight percent methylvinylidene isomer and having a numberaverage molecular weight in the range of about 400 to about 5,000; X ishydrogen, an alkali metal ion or alkyl having one to about 6 carbonatoms; W is —[CHR″]—_(m) wherein each R″ is independently H, alkylhaving one carbon atom to about 15 carbon atoms, or a substituted-alkylhaving one carbon atom to about 10 carbon atoms and one or moresubstituents selected from the group consisting of amino, amido, benzyl,carboxyl, hydroxyl, hydroxyphenyl, imidazolyl, imino, phenyl, sulfide,or thiol; and m is an integer from one to 4; Y is hydrogen, alkyl havingone carbon atom to about 10 carbon atoms, —CHR′OH, wherein R′ is asdefined above, or

wherein Y′ is —CHR′OH, wherein R′ is as defined above; and R, X, and Ware as defined above; Z is hydroxyl, a hydroxyphenyl group of theformula

wherein R, R₁, Y′, X, and W are as defined above, and n is an integerfrom 0 to 20, with the proviso that when n=0, Z must be

wherein R, R₁, Y′, X, and W are as defined above.
 46. The fuelcomposition of claim 45, wherein R is CH₂, R₁ is polyisobutyl groupderived from polyisobutene containing at least 50 weight percentmethylvinylidene isomer and having a number average molecular weight ofabout 700 to about 1,000, W is CHR″, wherein R″ is H, X is a sodium ionand n is an integer between 0 and
 20. 47. A fuel composition comprisinga major amount of hydrocarbons boiling in the gasoline or diesel rangeand a minor effective amount of one or more Mannich condensationproducts of claim
 15. 48. A fuel concentrate comprising an inert stableoleophilic organic solvent boiling in the range of from about 65° C. toabout 204° C. and from about 10 weight percent to about 90 weightpercent of one or more Mannich condensation products having the formula

wherein R is either CH₂ or CHR′ and wherein R′ is branched or linearalkyl having one carbon atom to about 10 carbon atoms, cycloalkyl havingfrom about 3 carbon atoms to about 10 carbon atoms, aryl having fromabout 6 carbon atoms to about 10 carbon atoms, alkaryl having from about7 carbon atoms to about 20 carbon atoms, or aralkyl having from about 7carbon atoms to about 20 carbon atoms, and R₁ is polyisobutyl derivedfrom polyisobutene containing at least 50 weight percentmethylvinylidene isomer and having a number average molecular weight inthe range of about 400 to about 5,000, X is hydrogen, an alkali metalion or alkyl having one carbon atom to about 6 carbon atoms, Y ishydrogen, alkyl having one carbon atom to about 10 carbon atoms,—CHR′OH, wherein R′ is as defined above, or

wherein Y′ is —CHR′OH, wherein R′ is as defined above; and R, X, and Ware as defined above; Z is hydroxyl, a hydroxyphenyl group of theformula

wherein R, R₁, Y′, X, and W are as defined above, and n is an integerfrom 0 to 20, with the proviso that when n=0, Z must be

wherein R, R₁, Y′, X, and W are as defined above.
 49. The fuelconcentrate of claim 48, wherein R is CH₂, R₁ is polyisobutyl having anumber average molecular weight of about 700 to about 1,000, W is CHR″,wherein R″ is H, X is a sodium ion and n is an integer between 0 and 20.50. A fuel concentrate comprising an inert stable oleophilic organicsolvent boiling in the range of from about 65° C. to about 204° C. andfrom about 10 weight percent to about 90 weight percent of one or moreMannich condensation products of claim 15.